Production of aluminum metal from alumina bauxites and clays by firstly producing a purified aluminum monochloride

ABSTRACT

In the production of aluminum monochloride from alumina, bauxites and clays wherein the produced aluminum monochloride gas stream contains at least CO 2  and Cl 2  and this gas stream is initially passed through at least one bed of reducing agent selected from the group consisting of charcoal and devolatilized coke to convert the CO 2  to CO; subsequently the gas stream now containing at least AlCl, CO and Cl 2  is contacted with molten aluminum metal to convert the Cl 2  to AlCl to produce a gas stream of which the major components are AlCl and CO substantially free of CO 2  and Cl 2 .

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of application Ser. No. 253,639 filed Apr. 13, 1981.

BACKGROUND OF THE INVENTION

The invention is primarily applicable to materials such as Bauxites and Clays that have present as major impurities iron and titanium in various mineral forms.

There has been a great deal of research and there is a vast quantity of literature in attempts to produce a relatively iron-free aluminum chloride from such raw materials as Bauxites and Clays. None of the processes proposed have been shown to be economically successful.

This problem can best be described by the following references: Landsberg "Chlorination Kinetics of Aluminum Bearing Minerals: Metallurgical Transactions B, Volume 6B, June 1975; pps. 207-208."

"Whereas Foley and Tittle showed that iron could be removed from pre-reduced bauxite by chlorination to produce a refractory grade alumina, FIG. 2 indicates that a substantial loss of alumina accompanies the initial rapid iron chlorination under reducing conditions. Even if this loss could be tolerated the remaining iron is too high for producing cell grade alumina or aluminum chloride."

U.S. Pat. No. 3,842,163, A. S. RUSSELL ET AL, entitled "Production of Aluminum Chloride" and assignors to Aluminum Company of America, state, to quote lines 45 to 58:

"In general, the reduction of aluminum-containing materials with chlorine in the presence of reducing carbon in some form to produce aluminum chloride is an old and generally well-known reaction and one of the suggested expedients referred to above utilized Bauxite as the alumina containing material. Bauxite however, normally contains many impurities including iron oxide, silica, and titania. Since these impurities readily react with chlorine in the presence of carbon to form iron, silicon, and titanium chlorides, the usual gaseous aluminum chloride reaction effluent therefrom must be subjected to cumbersome and expensive after-purification measures if these chloride contaminants are to be separated to provide even a reasonably pure aluminum product."

The U.S. Department of the Interior, Information Circular 1412 by Robert L. de Beauchamp, sums up the problem of producing AlCl₃ from various materials on page 6, the last paragraph reading as follows:

"The raw materials that may be used for the preparation of AlCl₃, include bauxite, clays, shale, anorthosite, coal ash, and many other aluminum containing materials. Bauxite or clays are the most logical choices because of their higher Al₂ O₃ contents and the large reserves of these materials available. Iron is the impurity most deleterious to the process since it uses up chlorine and is difficult to remove from the product."

Canadian Pat. No. 569,830 to Groth in 1939 described a method for chlorinating aluminiferous materials by treating dehydrated and crushed raw materials with aluminum chloride vapor at 600° C.-900° C., removing hot reaction gases containing iron chloride and titanium chloride, treating the residue with chlorine and a reducing agent, and processing the recovered aluminum chloride vapor containing silicon chloride and carbon monoxide at temperatures above 800° C. with alumina or aluminiferous materials free from iron and titanium. The gases recovered from the chlorination process are oxidized to convert at least the chlorides of iron and titanium to their oxides prior to condensation. Therefore, because of the oxidation step, chlorides of the materials are not recovered in reusable form. Further, the vapor mixture recovered cannot be diluted with CO in order that the oxidation stage can be carried out.

Groth Column 1, lines 28 to 32 states:

"It is true that when processing between 900° C.-1150° C. titanium is removed from the original material along with the iron in the form of titanium tetrachloride, but only in small amounts unless a large excess of aluminum chloride is used."

Weston, U.S. Pat. No. 4,277,446, in the first chlorination stage, depends upon the use of excess aluminum chloride containing FeCl₃ that is recovered from the circuit and returned to chlorinate the Fe₂ O₃. To quote, Column 8, lines 30-34:

"(b) Excess AlCl₃ that is used is recovered at a low cost as an impure AlCl₃ containing FeCl₃ and returned to the Number One Chlorination Stage without any deleterious effects on chlorinating the contained iron and titanium minerals."

SUMMARY OF THE INVENTION

It is accordingly a primary object of the present invention to provide a novel and low cost process for the production of aluminum metal and aluminum-silicon alloys substantially free of iron, titanium, and trace impurities that normally occur in economically applicable raw materials, such as Bauxites, Bauxitic Clays and Clays.

A further object of the present invention is to provide a novel and low cost process for the production of substantially pure aluminum metal from Bauxites, Bauxitic Clays, and Clays wherein the iron and titanium and trace impurities have previously been removed from the raw materials prior to the mass chlorination stage to produce aluminum monochloride. The aluminum monochloride, AlCl, is a necessary production step for the subsequent production of pure aluminum metal.

A still further object of the present invention is to provide a novel and low cost process for the production of aluminum metal from substantially pure alumina such as produced from the Bayer-Hall process.

Preferred stages in the process are:

(a) Calcining the feed material to remove free and chemically combined water, and where such minerals as Kaolinite are present to break the chemical bond of Al₂ O₃, SiO₂, and H₂ O, driving off the H₂ O as water vapor and forming amorphous Al₂ O₃ and amorphous SiO₂, which products respond differentially to chlorination treatment.

(b) At least One Chlorination Stage in which at least one agent is selected from the group consisting of Cl₂, COCl₂, SiCl₄, SiCl₂, AlCl₃ and AlCl, and in the presence of reducing agent selected from the group consisting of C, CO and CH and in the temperature range of about 750° C. to 1600° C. to differentially chlorinate at least the iron. Where substantially pure alumina is the feed material to the process this stage and the stage described at (c) are omitted.

(c) Following the at least One Chlorination Stage I subsequently raise the temperature of the residual solids containing the purified Al₂ O₃ -SiO₂ mixture to a temperature within the temperature range of about 1150° C. to about 1600° C., and preferably about 1200° C. to 1500° C. to remove non-volatile chlorides that may have formed at the lower temperature possibly used in the at least prior One Chlorination Stage. This is an optional stage in the process.

(d) At least a mass Chlorination Stage that involves mass chlorination of the Al₂ O₃ contained in the feed material, initially preferably using chlorine or COCl₂ in combination with a reducing agent preferably selected from the group consisting of carbon and carbon monoxide.

Following the initial mass chlorination of the Al₂ O₃ I subsequently produce AlCl₃ which I prefer to return either in toto or in part to this mass Chlorination Stage as at least part of the chlorinating agent.

Alternately I may use AlCl₃ as the total chlorinating agent to this mass Chlorination Stage and preferably at least AlCl₃ in combination with chlorination agent selected from the group consisting of Cl₂ and COCl₂.

Further, if the AlCl₃ produced in a subsequent treatment stage can be more economically disposed of by such means as a commercial product my chlorinating agent may be preferably selected from the group consisting of Cl₂ and COCl₂.

The preferred method of carrying out this Number Two Chlorination Stage is under reducing conditions.

The preferred temperature range in this stage is about 1200° C. to about 1500° C. In this temperature range aluminum monochloride is formed which in subsequent treatment forms the base for the production of pure aluminum metal.

(e) The gas stream produced by the chlorination stage described at (d) will contain major amounts of AlCl and CO₂, and minor amounts of Cl₂ with minor amounts of silicon chloride when treating such materials as bauxites and clays. The gas stream is passed through at least one bed of reducing agent selected from the group consisting of charcoal and devolatilized coke in the preferred temperature range of about 1200° C. to 1600° C. to convert the CO₂ to CO.

(f) The gas stream following the reducing agent treatment in (e) contains major quantities of AlCl and CO, and minor quantities of Cl₂ and possibly silicon chloride.

This gas stream is passed through a molten aluminum bath in the temperature range of preferably about 1200° C. to 1600° C. wherein the Cl₂ is converted to AlCl and silicon chloride, if present, to silicon metal and AlCl producing a gas stream containing AlCl and CO substantially free of Cl₂, CO₂, iron and silicon chloride.

(g) The gas stream produced in (f) is subjected to a condensation stage preferably in the temperature range of about 670° C. to 1050° C. to produce aluminum metal in the molten stage, or alternately below 660° C. to produce aluminum metal in the solid form.

The following will define for clarity various terms used in describing the invention:

Calcination--also known as debydration--this terminology as used in this application means the following:

(a) Removal of any free moisture as steam.

(b) Breaking down of the bond of water of crystallization in aluminum oxide minerals which have the chemical analysis of Al₂ O₃ xH₂ O, wherein a high percentage of water of crystallization is driven off as steam.

(c) Breaking down of the chemical bond or bonds of complex aluminum minerals such as Kaolinite, Al₂ O₃.2SiO₂.2H₂ O, wherein the H₂ O is driven off as steam and the Al₂ O₃ and SiO₂ are converted into amorphous Al₂ O₃ and amorphous SiO₂ respectively. To accomplish satisfactory calcination of Bauxites and Clays, a temperature range of 625° C. to about 1500° C. may be used. It will be appreciated that the effectiveness of the calcination step is primary function of temperature and time, the economic optimum being readily determined by anyone skilled in the Art.

This stage of the process uses conventional equipment well known in the Art, and consists of such equipment as horizontal rotary kilns, vertical shaft furnaces, and fluo-solids reactors with their auxiliary gas scrubbers and dust collection units.

Clays--generally refer to materials containing little or no Al₂ O₃.xH₂ O minerals and the major aluminum mineral component is essentially Kaolinite.

Iron and Titanium--the standard practice of the aluminum industry is to report Fe and Ti analyses as Fe₂ O₃ and TiO₂. The iron and titanium minerals contained in the aluminum bearing materials vary considerably and are but rarely only in the form of Fe₂ O₃ and TiO₂. For instance the major iron mineral in Arkansas Bauxite is siderite, FeCO₃, and the commonest occuring form of titanium is as ilmenite, FeOTiO₂. When I refer to percentages of Fe₂ O₃ and TiO₂ herein, I mean the chemical analyses of Fe and Ti converted to Fe₂ O₃ and TiO₂ respectively.

Carbon--any form of carbon that can be used in specific stages of the process of the invention as a reducing agent for the contained metallic oxides in the raw material used in the process herein described, and that will not introduce added impurities that may have a major detrimental effect on the final desired product.

Examples of such carbon are charcoal, devolatilized coal coke, and devolatilized petroleum coke. The type of coke used should be carefully selected to avoid introducing comparatively large quantities of impurities that may have a major detrimental effect in the process to produce pure aluminum monochloride.

Devolatilization--refers to solid fuels such as coal or petroleum coke wherein the specific material has been heated to a sufficiently high temperature to drive off substantially all of the contained water as water vapor and any free hydrogen contained in the raw material.

Neutral conditions--where there is just sufficient free oxygen to meet the needs of the reaction.

Oxidizing condition--where there is an excess of free oxygen to meet the needs of the reaction and free oxygen present at the end of the particular stage.

Reducing conditions--where there is an excess of free carbon CO, H₂, or CH radical present to meet the needs of the reaction.

Starvation or minor amounts of chlorination agent--this descriptive phrase, in the context of this patent, basically refers to small amounts of chlorination agent that is added to the circuit as either supplementary to a major chlorination agent or alternately by itself to normally chlorinate the impurities that occur in bauxites and clays with the exception of silica.

Aluminum trichloride--AlCl₃ or Al₂ Cl₆ or mixtures thereof.

Aluminum monochloride--AlCl

Aluminum chloride--AlCl₃, Al₂ Cl₆, & AlCl

Silicon tetrachloride--SiCl₄

Silicon dichloride--SiCl₂

Silicon Chloride--SiCl₄ and SiCl₂

Silica--SiO₂

Alumina--Al₂ O₃

BRIEF DESCRIPTION OF THE DRAWINGS

Reference is now made to the drawings accompanying the application where it will be seen that FIG. 1 shows a preferred flowsheet of the invention for the production of a purified AlCl gas stream containing major amounts of AlCl and CO and substantially free of CO₂, silicon chloride, and Cl₂.

FIG. 2 shows a preferred flowsheet of the invention treating the gaseous product produced by FIG. 1 to produce aluminum metal and aluminum silicon alloy metal.

DETAILED DESCRIPTION OF THE DRAWINGS

In FIGS. 1 and 2 the equipment used for handling of the solids is conventional such as fluo-solids reactors, horizontal rotary kilns, and shaft furnaces and for this reason is not shown in the drawings. Similarly the handling of the gases and the controlled temperature condensation, or condensation and fractional distillation to obtain separation of the various products is well known in such industries as the production of titanium oxide pigment from rutile or ilmenite using the chlorination process, and as such the equipment is not shown.

Similarly in FIG. 2 the maintaining of the molten bath of aluminum metal at controlled temperatures is well known in the Art and as such the equipment is not shown.

FIG. 1--The solids shown at 10, produced by pretreatment stages described herein or the Bayer process are substantially pure alumina, or Al₂ O₃ and SiO₂ substantially free of iron and other impurities.

The chlorination agents used in this stage as shown at 11 are preferably selected from the group consisting of AlCl₃, Cl₂, and COCl₂. The reducing agents used are preferably selected from the group consisting of charcoal, devolatilized coke and CO.

The temperature range is about 1200° C. to about 1600° C.

AlCl₃ when raised to this temperature range breaks down as follows:

    AlCl.sub.3 +temp. 1200° C. to 1600° C.--AlCl+Cl.sub.2

Chlorine and excess carbon react with the contained Al₂ O₃ as follows:

    2Al.sub.2 O.sub.3 +3C+2Cl.sub.2 -4AlCl+3CO.sub.2

In using closely controlled amounts of chlorine raidical the solids product shown at 13 discharging from this stage will be essentially SiO₂ with minor amounts of unchlorinated Al₂ O₃. This product will normally be waste as shown at 15.

The gas stream shown at 12 wherein the chlorination stage used little or no excess carbon to reduce all of the contained Al₂ O₃ the components of the gas stream will contain major amounts of AlCl and CO₂ with minor to trace amounts of silicon chloride, CO, and Cl₂ together with entrained solids of Al₂ O₃ and SiO₂.

As shown at 14 I prefer to remove the bulk of the entrained solids by mechanical means such as cyclones and drop boxes well known to the Art.

As shown at 17 the gas stream is passed through a carbon bed, preferably devolatilized coke or charcoal in the temperature range of about 1200° C. to about 1600° C. to convert substantially all of the contained CO₂ in the gas stream to CO. The chemical reaction is as follows:

    CO.sub.2 +C-2CO

This is an important step in the process as CO₂ present during the formation of aluminum metal as shown in FIG. 2 at 23 may cause oxidation of the aluminum metal by giving up one of its oxygens.

As shown at 19 the gas stream is passed through a molten bath of aluminum metal preferably in the temperature range of about 1200° C.-1600° C. Any contained silicon chloride in the gas stream reacts as follows:

    2Al+SiCl.sub.2 --2AlCl+Si.

The silicon thus produced will remain in the aluminum metal bath and tapped off together with aluminum metal to produce aluminum-silicon alloy.

The minor amount of free chlorine that may be present in the gas stream reacts as follows:

    2Al+Cl.sub.2 --2AlCl.

Thus the gas stream discharging from the molten aluminum bath as shown at 21 will be substantially AlCl and CO, substantially free of CO₂, Cl₂, iron and silicon.

At 14 the gas stream produced by the chlorination stage shown at 11 using excess carbon to reduce all of the contained Al₂ O₃ will contain major amounts of AlCl and CO with minor to trace amounts of silicon chloride and Cl₂ together with entrained solids. It may also contain minor amounts of CO₂.

In treating the gas stream shown at 12 I prefer to remove the bulk of the contained solids by mechanical means shown at 18.

As in the treatment of the gas stream shown at 12 the preferred step in this chlorination stage prior to the production of aluminum metal is the removal of any contained silicon chloride or Cl₂ by passing the gas stream through a molten aluminum metal bath shown at 21.

FIG. 2--As shown at 22 the feed stock to the pure aluminum metal production stage is substantially AlCl and CO.

The temperature of the gas stream as shown 51 is preferably in the temperature range of about 1250° C. to 1550° C.

This gas stream is fed into the aluminum metal condensation unit as shown at 23 wherein the temperature is reduced to within the temperature range of 670° C. to about 1050° C. With this temperature drop the following reaction takes place:

    3AlCl+Temp. 670° C.-1050° C.-AlCl.sub.3 +2Al.

As will be seen from this reaction two-thirds of the aluminum contained in the AlCl is recovered as aluminum metal. With all of the AlCl₃ produced cycled to the chlorination stage shown at 11, as the circuits come into metallurgical balance all of the contained aluminum in the produced AlCl as shown at 12 or 14 will be recovered as an aluminum-silicon alloy as shown at 19 and pure aluminum metal as shown at 30.

Following the condensation stage shown at 23 the gas stream will contain substantially pure AlCl₃ and CO as shown at 24.

The AlCl₃ is preferably condensed (not shown) at a temperature lower than 183° C.

All of the AlCl₃ can be cycled to the chlorination stage shown at 10 or alternately used in various required amounts in one or more prior chlorination stages as described in the examples. The CO component of the gas stream, in addition to a portion that may be cycled to the chlorination stage shown at 10 can be cycled to any of the preceeding stages including the calcination stage.

As shown at 27 the aluminum metal produced is in a molten state in the temperature range of 670° C. to about 1050° C., and in the solid form below 660° C.

As shown at 29 small quantities of entrained solids such as Al₂ O₃, SiO₂, and carbon can be removed by conventional means well known to the Art such as skimming and filtering to produce a purified aluminum metal as shown at 30.

EXAMPLES OF THE INVENTION IN REMOVING IRON AND OTHER IMPURITIES FROM BAUXITES AND CLAYS PRIOR TO THE MASS CHLORINATION OF THE CONTAINED ALUMINA

In the following examples to produce an alumina-silica product substantially free of iron, and subsequently aluminum chloride substantially free of iron, and finally aluminum metal from the aluminum chloride substantially free of iron EXAMPLES 1,2, and 3 illustrate three different methods to finally produce aluminum metal substantially iron free.

EXAMPLE 1 is two stage differential chlorination using SiCl₄ in the first stage and AlCl₃ in the second stage to differentially chlorinate the iron and titanium.

EXAMPLE 2 is single stage differential chlorination using at least one chlorination agent selected from the group consisting of HCl, Cl₂ and COCl₂, and at least one chlorination agent selected from the group consisting of AlCl₃, AlCl, SiCl₄ and SiCl₂, to differentially chlorinate at least the iron.

EXAMPLE 3 is single stage differential chlorination using at least one chlorination agent selected from the group consisting of Cl₂, COCl₂, AlCl₃, AlCl, SiCl₄ and SiCl₂ to differentially chlorinate at least the iron.

The following examples of the invention were carried out on a bulk sample of Kaolinitic Clay from a deposit located in the south eastern United States of America.

The sample as received was magnetically cobbed in a Colburne laboratory high intensity magnetic laboratory unit, dried to approximately 5% free moisture, crushed, put through a rolls and screened at 10 mesh and 100 mesh to produce a product that was essentially minus 10 plus 100 U.S. Standard. This product was calcined at 700° C. to 750° C., and after calcination was the feed material to the following examples except where otherwise noted.

The chemical analysis of the calcined product was as follows:

    ______________________________________                                         Al.sub.2 O.sub.3                                                                         SiO.sub.2                                                                             Fe.sub.2 O.sub.3                                                                            TiO.sub.2                                                                           L.O.I.                                      ______________________________________                                         44.0      51.5   1.27         2.77 0.3                                         ______________________________________                                    

All of the examples were carried out in a 21/2 inch fluosolids reactor using batch charges of 250 grams.

The total gas volume used in all tests was kept reasonably constant at 5.0 liters per minute calculated at 21.1° C., and adjusted to the 5.0 liters with CO.

EXAMPLE 1

The following were conditions of this example:

Temperature in stages one and two, 1010° C.

CO in both stages, adjusted to total gas volume of 5.0 liters/min.

Stage 1--SiCl₄ 0.7 gms/min. for 20 mins.

Stage 2--AlCl₃ 4.9 gms/min. for 40 mins.

The following results were obtained:

    ______________________________________                                         Chemical Analysis Solids                                                                              Gases                                                   % by Weight            % Distribution                                          Stage No.                                                                              Fe.sub.2 O.sub.3                                                                            TiO.sub.2 Fe.sub.2 O.sub.3                                                                       TiO.sub.2                               ______________________________________                                         1       0.021        0.494     98.35   82.1                                    2       0.012        0.273     99.05   90.15                                   ______________________________________                                    

In Stage 1 the SiCl₄ formed only approximately 2.0% of the gas stream and differentially chlorinated 98.35% of the Fe₂ O₃ and 82.1% of the TiO₂. All of the SiCl₄ could be chemically accounted for in the reactions with the Fe₂ O₃ and TiO₂ resulting in no requirement for recirculation of any excess chlorination agent such as in the Weston U.S. Pat. No. 4,277,446.

This was an amazing result in a twenty minute differential chlorination period.

The following are the chemical reactions involved:

    2Fe.sub.2 O.sub.3 +3SiCl.sub.4 -4FeCl.sub.3 +3.SiO.sub.2

    TiO.sub.2 +SiCl.sub.4 -TiCl.sub.4 +SiO.sub.2

In using CO as the main fluidizing agent the outstanding metallurgy using SiCl₄ as the chlorination agent could not be duplicated using CO₂.

Further, in using appreciably higher concentrations of SiCl₄ the results could not be duplicated. There seems to be no logical explanation for this totally unexpected phenomenon.

The maximum concentration of SiCl₄ in the gas stream for optimum results is approximately 10%.

In Stage 2 of the process the final product shows 99.05% of the Fe₂ O₃ and 90.25% of the TiO₂ differentially chlorinated.

Not only does this product meet unheard of Fe₂ O₃ specifications for the highest grade refractory, but in addition, following mass chlorination of the contained Al₂ O₃ and differential temperature condensation of the AlCl₃ would produce acceptably pure aluminum metal.

EXAMPLE 2

The following were conditions of this example:

Temperature in Number One Chlorination Stage, 913° C.

Agents Used:

1.5 gms/min. HCl and

1.0 gms/min. SiCl₄ and make-up of gas stream to approximately 5.0 liters/min. with CO.

Treatment time: 25 mins.

At the end of the 25 minute treatment of the solids feed the residual solids product analyzed 0.016% Fe₂ O₃. This analysis shows that 98.7% of the Fe₂ O₃ in the feed material was chlorinated to produce a substantially iron free alumina silica product.

This was an amazing result from the use of starvation quantities of HCl and SiCl₄ and the short duration of the differential chlorination treatment. The alumina-silica product is outstanding in the low iron content and subsequent production of substantially iron-free aluminum chloride product suitable for the production of aluminum metal.

EXAMPLE 3

The following were conditions of this example:

Temperature in Number One Chlorination Stage, 975° C.

Agents used: 1.06 gms/min. Cl₂ and make-up of gas stream to approximately 5.0 liters/min. with CO.

Treatment time: 20 mins.

At the end of the 20 minute treatment of the solids feed the residual solids product analyzed 0.022% Fe₂ O₃. This analysis shows that 98.3% of the Fe₂ O₃ in the feed material was chlorinated to produce a substantially iron free alumina silica product.

This was an outstanding result from the use of starvation quantities of Cl₂ and the short duration of the differential chlorination treatment. The Alumina-silica product is outstanding in the low iron content and in the subsequent production of aluminum chloride, the aluminum chloride produced would be substantially iron free, and suitable for the production of aluminum metal.

The invention has been described herein with references to certain preferred embodiments. However, as obvious variations thereon will become apparent to those skilled in the Art, the invention is not considered to be limited thereto. 

What I claim as my invention is:
 1. The process steps for the production of aluminum metal from the group of materials consisting of alumina, bauxites and clays and said materials containing at least Al₂ O₃ minerals in the group consisting of Al₂ O₃ xH₂ O and Al₂ O₃.2SiO₂ 2H₂ O and free moisture and said Al₂ O₃ minerals containing chemically combined H₂ O comprising: subjecting the said materials to calcination in the temperature range of about 625° C. to 1500° C. to produce a calcined product substantially free of said chemically combined H₂ O and said free moisture; subsequently subjecting the said calcined product to at least a mass chlorination stage in the presence of chlorination agent selected from the group consisting of Cl₂, COCl₂, and AlCl₃ and reducing agent selected from the group consisting of C and CO and in the temperature range of about 1200° C. to 1600° C. to produce a gas stream wherein the said Al₂ O₃ has been converted to gaseous AlCl and said gas stream contains said AlCl, and at least CO₂ and Cl₂ ; subsequently passing the said gas stream through at least one bed selected from the group consisting of charcoal and devolatilized coke and in the temperature range of about 1200° C. to 1600° C. to convert said CO₂ to CO to produce a first modified gas stream containing at least said AlCl and Cl₂, and said CO; subsequently passing the said first modified gas stream through molten aluminum metal in the temperature range of about 1200° C. to 1600° C. to convert the said Cl₂ to AlCl to produce a second modified gas stream containing at least the said AlCl and CO; subsequently lowering the temperature of the said second modified gas stream to within the temperature rang of about 670° C. to 1050° C. to produce molten aluminum metal and a third modified gas stream containing AlCl₃ and said CO.
 2. The process of claim 1 wherein the said second modified gas stream containing AlCl and CO is lowered to below 660° C. to produce the said aluminum metal as a solid.
 3. The process of claim 1 wherein the said mass chlorination stage is carried out in the presence of catalyst and said catalyst is selected from the group consisting of NaAlCl₄, KAlCl₄, NaCl and KCl.
 4. The process of claim 1 wherein preceding the said calcination the said materials are prepared to produce particles in the range of about 10 to 100 mesh.
 5. The process of claim 2 wherein at least part of the said third modified gas stream containing AlCl₃ and CO is cycled to said mass chlorination stage.
 6. The process steps for the production of aluminum metal from the group of materials consisting of bauxites and clays and said materials containing at least iron minerals and at least Al₂ O₃ minerals in the group consisting of Al₂ O₃ xH₂ O and Al₂ O₃.2SiO₂.2H₂ O and free moisture and said Al₂ O₃ minerals containing chemically combined H₂ O comprising: subjecting the said materials to calcination in the temperature range of about 625° C. to 1500° C. to produce a calcined product substantially free of said chemically combined H₂ O and said free moisture; subsequently subjecting the said calcined product to at least one chlorination stage in the presence of chlorination agent selected from the group consisting of Cl₂, COCl₂, AlCl₃, AlCl, SiCl₄ and SiCl₂ and reducing agent selected from the group consisting of C and CO and in the temperature range of about 750° C. to 1500° C. to produce a solids Al₂ O₃ -SiO₂ product substantially free of said iron; subsequently subjecting the said Al₂ O₃ -SiO₂ product to at least a mass chlorination stage in the presence of chlorination agent selected from the group consisting of Cl₂, COCl₂, and AlCl₃ and reducing agent selected from the group consisting of C and CO and in the temperature range of about 1200° C. to 1600° C. to produce a gas stream wherein the said Al₂ O₃ has been converted to gaseous AlCl and said gas stream contains the said AlCl, and at least CO₂, CL₂ and silicon chloride; subsequently passing the said gas stream through at least one bed selected from the group consisting of charcoal and devolatilized coke and in the temperature range of about 1200° C. to 1600° C. to convert said CO₂ to CO and to produce a first modified gas stream containing at least said AlCl, Cl₂ and silicon chloride and said CO; subsequently passing the said gas stream through molten aluminum metal in the temperature range of about 1200° C. to 1600° C. to convert the said Cl₂ to AlCl and said silicon chloride to silicon and AlCl to produce a second modified gas stream containing at least AlCl and CO and said silicon remaining in the said molten aluminum metal; subsequently lowering the temperature of the said second modified gas stream to within the temperature range of about 670° C. to 1050° C. to produce molten aluminum metal and a third modified gas stream containing at least AlCl₃ and said CO.
 7. The process of claim 6 wherein the said second modified gas stream containing AlCl and CO is lowered to below 660° C. to produce the said aluminum metal as a solid.
 8. The process of claim 6 wherein the said mass chlorination stage is carried out in the presence of catalyst and said catalyst is selected from the group consisting of NaAlCl₄, KAlCl₄, NaCl and KCl.
 9. The process of claim 6 wherein preceding the said calcination the said materials are prepared to produce particles in the range of about 10 mesh to 100 mesh.
 10. The process of claim 6 hwerein at least part of the said third modified gas stream containing AlCl₃ and CO is cycled to said mass chlorination stage. 